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CN1980739A - Method and apparatus for mass analysis of samples - Google Patents

Method and apparatus for mass analysis of samples Download PDF

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Publication number
CN1980739A
CN1980739A CN200580022251.9A CN200580022251A CN1980739A CN 1980739 A CN1980739 A CN 1980739A CN 200580022251 A CN200580022251 A CN 200580022251A CN 1980739 A CN1980739 A CN 1980739A
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array
sample
microbalance
samples
shuttle
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R·文德尔博
D·E·阿克波力亚
A·卡尔松
I-R·乔安森
I·M·达尔
B·G·菲斯曼
R·布洛姆
D·T·王
M·古里克森
M·普拉森
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Honeywell UOP LLC
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/02Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/02Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations
    • G01N35/028Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations having reaction cells in the form of microtitration plates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00Chemistry: analytical and immunological testing
    • Y10T436/24Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00Chemistry: analytical and immunological testing
    • Y10T436/25Chemistry: analytical and immunological testing including sample preparation

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

The invention includes an apparatus and method for mass analysis of each of an array of samples contained in separate sample containers (18, 18'). The sample container (18, 18') is placed on or suspended from a plurality of sensors (19, 19', 19", 19" ') which preferably comprise an array of microbalances which provide output signals comprising mass data for the sample array.

Description

样品的质量分析方法和装置Sample mass analysis method and device

发明背景Background of the invention

本发明涉及一阵列样品质量特性的同时测量。更具体地,本发明涉及在微克至克范围内、以及在更高或更低的范围内测定一阵列样品的质量。The present invention relates to the simultaneous measurement of mass characteristics of an array of samples. More specifically, the invention relates to determining the mass of an array of samples in the microgram to gram range, and in higher and lower ranges.

实验室规模的重力测量已经受到相对笨重的设备和低效率的测量速度的阻碍。需要更有效的监控并记录大量材料的质量的方法,以评测候选物性能和/或筛选和选择用于进一步开发的最佳候选物。Laboratory-scale gravity measurements have been hampered by relatively bulky equipment and inefficient measurement speeds. More efficient methods of monitoring and recording the quality of large quantities of material are needed to evaluate candidate performance and/or screen and select the best candidates for further development.

用于催化剂和吸附剂之类用途的材料的最优化通常要求尽可能快速地表征大量此类材料样品。这种表征的分析技术必须又快又精确,以处理大量与最优化有关的数据。并行而不是连续测量有利于快速生成用于这种表征的数据。这些测量特别可用于测定例如表面积和孔径之类的表面性能,它们在多种应用中是潜在性能的指征。The optimization of materials for applications such as catalysts and adsorbents often requires the characterization of large numbers of samples of such materials as quickly as possible. Analytical techniques for such characterization must be fast and accurate to handle the large volumes of optimization-related data. Parallel rather than serial measurements facilitate rapid generation of data for such characterization. These measurements are particularly useful for determining surface properties such as surface area and pore size, which are indicators of potential performance in a variety of applications.

过去十年来,微切削加工技术已经被广泛应用。硅微切削加工特别能够实现机械元件和传感元件的完全集成,为成本有效地生产小型转换器提供了将传感器阵列制造成单个集成单元的可能。Over the past decade, micromachining technology has been widely used. Silicon micromachining in particular enables the full integration of mechanical and sensing elements, opening up the possibility of fabricating sensor arrays as a single integrated unit for the cost-effective production of small transducers.

专利公开US 2002/0028456 A1公开了一种排列在基材上以测量沉积在该基材上的样品的各种材料特性的传感器阵列。样品可以以溶液方式或通过气相淀积沉积在传感器上。能够测量的性能包括温度、热容、热导率、热稳定性、介电常数、粘度、密度、弹性、电容和磁性能。Patent publication US 2002/0028456 A1 discloses an array of sensors arranged on a substrate to measure various material properties of a sample deposited on the substrate. Samples can be deposited on the sensor in solution or by vapor deposition. Properties that can be measured include temperature, heat capacity, thermal conductivity, thermal stability, dielectric constant, viscosity, density, elasticity, capacitance, and magnetic properties.

WO 00/20850描述了用于气态或蒸气态分析物的重量法化学测量的多传感器装置,其包括基材和多个由压电元件制成的传感器,压电元件在基材上通过厚膜技术获得。传感器涂有用于吸收分析物的敏感涂层。WO 00/20850 describes a multisensor device for the gravimetric chemical measurement of gaseous or vaporous analytes comprising a substrate and a plurality of sensors made of piezoelectric elements mounted on the substrate through thick film Technology acquired. The sensor is coated with a sensitive coating that absorbs the analyte.

US 5,983,711公开了温控重量法湿度分析仪,其包括连接到称重装置上的样品容器、温度传感器和响应该温度传感器输出信号的加热器及控制器。但是,该专利没有公开称重装置阵列。US 5,983,711 discloses a temperature-controlled gravimetric humidity analyzer comprising a sample container connected to a weighing device, a temperature sensor, a heater and a controller responsive to the output signal of the temperature sensor. However, this patent does not disclose an array of weighing devices.

WO 03/071241公开了用于微量称重的弹簧秤,其包括通过周围框架中的至少三个挠性弹簧悬挂的装载平台,具有用于测量挠性弹簧一侧上的应变的桥接应变仪。但并未提出称重装置阵列。WO 03/071241 discloses a spring balance for microweighing comprising a loading platform suspended by at least three flexible springs in a surrounding frame, with bridge strain gauges for measuring the strain on one side of the flexible springs. However, an array of weighing devices is not proposed.

US 4,566,326提出了自动吸附和解吸分析仪,其使用带有相联的阀、控制器和传感器的多个样品槽对多个粉末样品进行测量。该分析仪可以在多个样品上几乎同时测量表面积、总孔体积、微孔体积、平均孔半径、和孔径大小和表面积分布。这种分析仪代表了实现本发明目的的已知技术。US 4,566,326 proposes an automated sorption and desorption analyzer using multiple sample cells with associated valves, controllers and sensors to perform measurements on multiple powder samples. The analyzer can nearly simultaneously measure surface area, total pore volume, micropore volume, average pore radius, and pore size and surface area distribution on multiple samples. Such analyzers represent known art for the purpose of the present invention.

但是,该技术没有提出对独立样品容器中所含的一阵列样品进行质量分析的装置或方法。However, the art does not address a device or method for mass analysis of an array of samples contained in individual sample containers.

发明概要Summary of the invention

本发明提供了对一阵列独立的样品容器中所含的一阵列样品的每一个进行质量分析的装置和方法,放置这些样品容器使其与多个传感器相互作用,所述传感器提供包括该样品阵列的质量数据的输出信号。通过这种分析,本发明能够快速测定与样品质量有关的各种样品特性。还加快了其它样品阵列的后续分析。The present invention provides apparatus and methods for mass analysis of each of an array of samples contained in an array of individual sample containers positioned to interact with a plurality of sensors providing The output signal of the quality data. Through this analysis, the present invention enables rapid determination of various sample properties related to sample quality. Subsequent analyzes of other sample arrays are also expedited.

在更具体的实施方案中,本发明提供了对一阵列样品的每一个进行质量分析的装置,其包括一阵列不同的容纳样品的样品容器,放置这些容器使其与多个微量天平相互作用,所述传感器提供包括该样品阵列的质量数据的输出信号。In a more specific embodiment, the present invention provides an apparatus for performing mass analysis of each of an array of samples comprising an array of distinct sample containers containing samples positioned to interact with a plurality of microbalances, The sensor provides an output signal comprising mass data for the sample array.

在再具体的实施方案中,本发明提供了对一阵列样品的每一个进行质量分析的装置,其包括一阵列不同的容纳样品的样品容器,放置这些容器使其与多个弹簧秤相互作用,所述传感器提供包括该样品阵列的质量数据的输出信号。In yet another specific embodiment, the present invention provides an apparatus for mass analysis of each of an array of samples comprising an array of distinct sample containers containing samples positioned to interact with a plurality of spring balances such that The sensor provides an output signal comprising mass data for the sample array.

在另一具体实施方案中,本发明提供了对一阵列样品的每一个进行质量分析的装置,其包括一阵列容纳样品的篮筐,放置这些篮筐使其与多个微量天平相互作用,所述传感器提供包括该样品阵列的质量数据的输出信号。In another embodiment, the present invention provides an apparatus for mass analysis of each of an array of samples comprising an array of sample-holding baskets positioned to interact with a plurality of microbalances such that The sensor provides an output signal comprising mass data for the sample array.

在另一实施方案中,本发明提供了如下对一阵列样品进行质量分析的方法:将该样品阵列置于一阵列独立的样品容器中,放置样品容器使其与提供包括该样品阵列的质量数据的输出信号的多个传感器相互作用,并根据输出信号测定各个样品的质量。In another embodiment, the present invention provides a method of mass analyzing an array of samples by placing the array of samples in an array of individual sample containers, positioning the sample containers so that they are compatible with providing mass data comprising the array of samples The output signals of multiple sensors interact, and the quality of each sample is determined based on the output signals.

在更具体的另一实施方案中,本发明提供了如下对多个样品进行质量分析的方法:将样品置于一阵列独立的样品容器中,放置样品容器使其与提供包括该样品阵列的质量数据的第一输出信号的多个传感器相互作用,然后将该样品阵列置于改变的环境条件中,然后测量来自该样品阵列的第二输出信号,并通过比较在环境条件改变之前和之后来自该样品阵列的输出信号确定各个样品的一个或多个性质。In another more specific embodiment, the present invention provides a method for mass analysis of a plurality of samples by placing the samples in an array of individual sample containers, placing the sample containers such that they are compatible with providing a mass comprising the array of samples. A plurality of sensors interacting with a first output signal of data, then subjecting the sample array to a changed environmental condition, then measuring a second output signal from the sample array, and by comparing the output signal from the sample array before and after the environmental condition change The output signal of the sample array determines one or more properties of each sample.

附图的简要说明Brief description of the drawings

图I显示了本发明装置较广泛的实施方案,该装置包括六个样品托盘的小阵列,它们与相同数量的多个传感器相互作用。Figure 1 shows a broader embodiment of the device of the invention comprising a small array of six sample trays interacting with the same number of sensors.

图II显示了在阵列单元中包含弹簧秤的实施方案中的本发明装置。Figure II shows the device of the invention in an embodiment comprising spring balances in the array unit.

图III显示了可用于质量分析的桥接电路的例子。Figure III shows an example of a bridge circuit that can be used for mass analysis.

图IV是与基底部件相联的弹簧秤的截面侧视图。Figure IV is a cross-sectional side view of a spring balance associated with a base member.

图V显示了在阵列单元中包含悬挂筐的实施方案中的本发明装置。Figure V shows the device of the present invention in an embodiment comprising hanging baskets in the array unit.

图VI-A和VI-B显示了微量天平作为悬臂的另一装配方式。Figures VI-A and VI-B show another arrangement of the microbalance as a cantilever.

发明详述Detailed description of the invention

总体而言,本发明提供了对一阵列独立的样品容器中所含的一阵列样品的每一个进行质量分析的装置和方法,放置这些样品容器使其与多个传感器相互作用,所述传感器提供包括该样品阵列的质量数据的输出信号。尽管该方法和相关装置的基本要素以单数形式描述,但要理解的是,各种基本要素或整个装置的两个或多个并联或串联的组合也在本发明的范围内。In general, the present invention provides apparatus and methods for mass analysis of each of an array of samples contained in an array of individual sample containers positioned to interact with a plurality of sensors that provide An output signal comprising mass data for the sample array. Although elements of the method and associated apparatus are described in the singular, it is to be understood that combinations of two or more of the various elements or of the entire apparatus in parallel or in series are also within the scope of the invention.

样品和样品容器“阵列”包括至少4个、更通常6个或更多、通常至少8个、,任选48个或更多样品和容器。在该阵列中包含这些数的一定倍数,例如按照类似于微滴定盘的行列形式排列的24、96、392或1264,这也在本发明的范围内。优选地,样品容器在空间上分离,以使该阵列的各个成员可分开编址。传感器的“多个”在如上对“阵列”所述相同的数值范围内,且优选地,传感器数量与样品和样品容器的数量相同。与使用并行或连续分析的已知技术相对地考虑本发明,根据已知技术进行分析所需的设备较为昂贵和/或时间较多。An "array" of samples and sample containers includes at least 4, more typically 6 or more, typically at least 8, optionally 48 or more samples and containers. It is also within the scope of the invention to include certain multiples of these numbers in the array, for example 24, 96, 392 or 1264 arranged in rows and columns similar to microtiter plates. Preferably, the sample containers are spatially separated such that individual members of the array are separately addressable. A "plurality" of sensors is within the same numerical ranges as described above for an "array", and preferably the number of sensors is the same as the number of samples and sample containers. The present invention is considered in contrast to known techniques using parallel or sequential analysis, according to which the equipment required for analysis is relatively expensive and/or time consuming.

“样品”是指需要进行质量分析的基材。这些基材通常是固体,但不必限定为固体材料,例如可以是液体、凝胶、浆液等。液体应用的可行例子是在离子液体、监测液体中的气体溶度等方面。固体样品的可行例子包括但不限于陶瓷、分子筛、其它无机化合物、复合材料、金属和金属合金、金属互化物、碳、离子固体、分子固体、共价网络固体、有机金属材料、有机聚合物和它们的组合。表面性质对其而言重要的物质是优选的,尤其优选的物质包括金属氧化物、分子筛和催化剂。"Sample" refers to a substrate to be subjected to mass analysis. These substrates are generally solid, but need not be limited to solid materials, such as liquids, gels, slurries, and the like. Viable examples of liquid applications are in ionic liquids, monitoring gas solubility in liquids, etc. Possible examples of solid samples include, but are not limited to, ceramics, molecular sieves, other inorganic compounds, composite materials, metals and metal alloys, intermetallic compounds, carbon, ionic solids, molecular solids, covalent network solids, organometallic materials, organic polymers, and their combination. Substances for which surface properties are important are preferred, and particularly preferred substances include metal oxides, molecular sieves and catalysts.

样品形式对于本发明的定义而言并不关键。如果是固体材料,则样品可以是单个固体整料,或作为粒子、膜、板、盘、珠、球、杆状、线或任何适合进行分析的形式。优选地,固体样品是微粒形式,尤其优选的是样品的细粉形式。在细粉中,平均粒度通常为0.01微米至1000微米,更通常为0.1微米至100微米。The sample form is not critical to the definition of the invention. If a solid material, the sample may be a single solid monolith, or as a particle, film, plate, disk, bead, sphere, rod, wire, or any form suitable for analysis. Preferably, the solid sample is in particulate form, especially preferred is the sample in fine powder form. In fine powders, the average particle size is typically from 0.01 micron to 1000 microns, more typically from 0.1 micron to 100 microns.

本发明包括一阵列的样品容器,其中为各个待分析样品提供样品容器或容器。样品容器可以是可容纳样品并可移至和移离下文定义的传感器的任何设备。优选地,样品容器或容器提供了朝上的凹面,其容纳样品而没有显著溢出危险。合适的构造包括但不限于盘、杯、碟、板、凹入处和凹坑。或者,样品容器可以包括篮筐,其被钩子、绳圈、环、夹子、扣钧或其它紧固件支承在传感器上。将样品置于样品容器中以移至和移离传感器的优点包括:The present invention includes an array of sample containers, wherein a sample container or containers are provided for each sample to be analyzed. A sample container may be any device that can hold a sample and that can be moved to and from a sensor as defined below. Preferably, the sample container or container provides an upwardly facing concave surface which accommodates the sample without significant risk of spillage. Suitable formations include, but are not limited to, plates, cups, saucers, plates, recesses and wells. Alternatively, the sample container may include a basket that is supported on the sensor by hooks, loops, loops, clips, clasps, or other fasteners. The advantages of placing the sample in the sample container to move to and from the sensor include:

*避免传感器由于与样品直接接触而污染,和 * Avoid contamination of the sensor due to direct contact with the sample, and

*能够通过多组样品容器在样品装卸和样品容器清洁的同时进行测量。 * Ability to perform measurements simultaneously with sample loading and unloading and sample container cleaning with multiple sets of sample containers.

不会对分析结果产生负面影响的任何材料均适合用于样品容器。优选地,样品容器的与样品接触的表面在分析方法的所有条件下均对样品稳定和惰性。对于样品容器,陶瓷和金属材料之一或这两种尤为优选。Any material that does not adversely affect the analytical results is suitable for the sample container. Preferably, the surface of the sample container which comes into contact with the sample is stable and inert to the sample under all conditions of the analytical method. For sample containers, one or both of ceramic and metallic materials are particularly preferred.

任选地,通过样品容器提供该分析的输入物。例如,但非限制性地,样品容器可以包含导热材料,通过该材料为样品提供热量或测量样品温度。或者,可以通过样品容器将电能传递到样品上。通过物理或化学作用将样品容器用有助于分析的材料涂布或分层,这也在本发明的范围内。此外,样品本身可以通过物理或化学结合、蒸发等涂布到样品容器表面上。Optionally, inputs to the assay are provided via sample containers. For example, and without limitation, the sample container may contain a thermally conductive material through which heat is supplied to the sample or the temperature of the sample is measured. Alternatively, electrical energy can be delivered to the sample through the sample container. It is also within the scope of the present invention to physically or chemically coat or layer the sample container with a material that facilitates the analysis. In addition, the sample itself can be applied to the surface of the sample container by physical or chemical bonding, evaporation, and the like.

在样品阵列的分析之后,可以将每一个已分析过的样品从各样品容器上卸载,然后在该样品容器阵列中装入新的一阵列样品。优选地,在进行分析的同时已经在附加样品容器中制备一个或多个附加的样品阵列,从而可以在将被分析的样品从各样品容器上卸载的同时,安放该附加的样品阵列使其与多个传感器相互作用。该样品容器阵列最好包含在可以朝包含传感器的装置下降的托盘中,以使样品容器在传感器上放置就位。由此,样品的制备和卸载不会延缓样品分析,并更有效地利用包含传感器的装置。Following analysis of the array of samples, each analyzed sample may be unloaded from each sample container and the array of sample containers loaded with a new array of samples. Preferably, one or more additional sample arrays have been prepared in additional sample containers while the analysis is being performed, so that the additional sample arrays can be positioned in conjunction with the Multiple sensors interact. The array of sample containers is preferably contained in a tray that can be lowered towards the device containing the sensor to place the sample containers in place on the sensor. Thus, sample preparation and unloading do not delay sample analysis and more efficient use is made of the device containing the sensor.

图I显示了六个独立样品容器的阵列1,放置这些样品容器使其与提供包括该样品阵列的质量数据的输出信号的六个传感器相互作用。对于六个样品容器和弹簧秤的各个单元,传感器均包含如下所述的容纳在框架2中的弹簧秤19。如上所述,“阵列”或“多个”包含至少4组并优选更大数量的这样的单元。Figure 1 shows an array 1 of six individual sample containers positioned to interact with six sensors providing output signals comprising mass data for the sample array. For each unit of six sample containers and spring balances, the sensor comprises a spring balance 19 housed in the frame 2 as described below. As noted above, an "array" or "plurality" comprises groups of at least 4 and preferably greater numbers of such elements.

合适的传感器包括可以测量质量变化并支承样品容器的任何类型的传感器。传感器材料包括金属、硅、其它半导体材料、玻璃、碳、聚合物、膜和类似物中的一种或多种,其中硅之类的半导体材料特别优选。本发明的优选传感器包括微量天平,特别是如国际公开WO 03/071241中所述的弹簧秤,该公开完全经此引用并入本文。优选的弹簧秤19包含通过至少三个挠性弹簧悬挂在周围框架中的装载平台,具有用于测量挠性弹簧一侧上应变的桥接应变仪。Suitable sensors include any type of sensor that can measure changes in mass and support a sample container. Sensor materials include one or more of metals, silicon, other semiconductor materials, glass, carbon, polymers, films, and the like, with semiconductor materials such as silicon being particularly preferred. Preferred sensors of the invention include microbalances, particularly spring balances as described in International Publication WO 03/071241, which disclosure is hereby incorporated by reference in its entirety. A preferred spring scale 19 comprises a loading platform suspended in a surrounding frame by at least three flexure springs, with bridge strain gauges for measuring strain on one side of the flexure springs.

图II示意性显示了本发明的优选实施方案的上视图。在该例子中,弹簧秤19具有正方形,在其中心具有装载平台1,装载平台1上放置如图I中所示的样品容器。通过挠性杆(flexural beams)或挠性弹簧3将装载平台1悬挂在框架2中,这些杆/弹簧在所示例子中沿装载平台的各侧边排列,且已经蚀刻或机械加工出狭缝5和6以提供挠性杆,从而使狭缝在挠性杆3外具有一个狭缝部分5,并在下一挠性杆3内具有连续部分6。在这种构造中,挠性杆3变得相对较长和顺从,即,装载平台1可以产生深摆动。各挠性杆3位于框架2和装载平台1之间的间隙中,该间隙是由狭缝部分5和6界定的。每一挠性杆3具有与装载平台1的接点7,其正对着相邻挠性杆与框架2的接点8。使用传感器记录装载平台1上的载荷,标记4代表用于此用途的应变仪。当将样品容器置于装载平台1上时,该平台向远离观察者的方向下沉,且挠性杆3弯曲并呈现与浅S类似的形状。然后装载平台将沿着与装载平台面垂直的轴略微旋转,因为杆3的长度基本保持恒定。Figure II schematically shows a top view of a preferred embodiment of the invention. In this example, the spring scale 19 has a square shape with a loading platform 1 in its center on which the sample containers as shown in FIG. 1 are placed. The loading platform 1 is suspended in the frame 2 by means of flexural beams or flexural springs 3 which in the example shown are arranged along each side of the loading platform and have slots etched or machined 5 and 6 to provide a flexible rod such that the slot has one slit portion 5 outside the flexible rod 3 and a continuous portion 6 in the next flexible rod 3 . In this configuration, the flexible rod 3 becomes relatively long and compliant, ie the loading platform 1 can generate deep swings. Each flexible rod 3 is located in the gap between the frame 2 and the loading platform 1 , which gap is delimited by the slit portions 5 and 6 . Each flexible rod 3 has a joint 7 with the loading platform 1 , which is directly opposite the joint 8 of the adjacent flexible rod with the frame 2 . A sensor is used to record the load on the loading platform 1, reference 4 represents the strain gauge used for this purpose. When the sample container is placed on the loading platform 1 , the platform sinks away from the observer, and the flexible rod 3 bends and assumes a shallow S-like shape. The loading platform will then rotate slightly along an axis perpendicular to the loading platform surface, since the length of the rod 3 remains substantially constant.

当在平台上装载时,由于挠性杆3的上述S形状,在与框架2和装载平台1相交的区域(即在接点7和8处)发现杆中最强的机械应力。因此,例如,如图II所示安装应变仪4是有利的。或者,应变仪可以安装在与装载平台的交叉点而非与框架的交叉点上,但是这需要较长的来自应变仪并通往信号处理设备的引线。在如图II所示安装应变仪4的方式中,所有四个应变仪均以相同方向安装以优化惠斯登电桥中传感器的连接。或者,传感器/应变仪可以以不同方向安装;例如在改变桥接的情况下,将其中两个相对于另外两个旋转90°。When loaded on the platform, due to the above-mentioned S-shape of the flexible rod 3, the strongest mechanical stresses in the rod are found in the area where the frame 2 and the loading platform 1 intersect (ie at the joints 7 and 8). Thus, for example, it is advantageous to mount the strain gauges 4 as shown in FIG. II. Alternatively, the strain gauges could be mounted at the intersection with the loading platform instead of the frame, but this would require longer leads from the strain gauges to the signal processing equipment. In the manner in which the strain gauges 4 are mounted as shown in Figure II, all four strain gauges are mounted in the same orientation to optimize the connection of the sensors in the Wheatstone bridge. Alternatively, the sensors/strain gauges can be mounted in different orientations; for example two of them rotated by 90° relative to the other two in case of changing the bridge.

应变仪4可以通过沉积和图案形成、或通过胶接现成的电阻器作为分离的传感器安装在所述交叉点(接点8或7)的顶部。或者,压电电阻器形式的应变仪可以制造成有利的硅结构整体中的一部分,或作为表面元件以任何合适的方式安装。The strain gauge 4 can be mounted on top of the junction (junction 8 or 7) as a separate sensor by deposition and patterning, or by gluing off-the-shelf resistors. Alternatively, strain gauges in the form of piezoresistors may be fabricated as part of an advantageous silicon structural integrity, or mounted as surface elements in any suitable manner.

在本发明的有利实施方案中,将装载平台、挠性弹簧和框架成形为半导体材料的一种微切削加工或蚀刻的部件;该材料最好是硅。安装在挠性弹簧与框架或装载平台之间的交叉点的应变仪(优选压电电阻器)可以整合在该固体材料部件中。因此,主要用于制造弹簧秤的半导体材料也可用于制造用于检测载荷的传感器元件。In an advantageous embodiment of the invention, the loading platform, flexible spring and frame are formed as a micromachined or etched part of a semiconductor material; preferably silicon. Strain gauges (preferably piezoresistors) mounted at the intersections between the flexible springs and the frame or loading platform may be integrated in this solid material part. Therefore, semiconductor materials that are mainly used in the manufacture of spring balances can also be used in the manufacture of sensor elements for detecting loads.

图III显示了可用于通过本发明的秤提供质量分析的桥接电路。所示桥接电路是适用于图II的情况的惠斯登电桥,其中每一应变仪4以相同方向安装。应变仪4是电阻器形式,并且惠斯登电桥桥接电路通过电源(电池)11和测量仪器12完成。这是标准类型的电路,但也可以与具有其它应变仪构造的其它实施方案结合使用其它桥接电路变体。Figure III shows a bridge circuit that can be used to provide mass analysis by the scale of the present invention. The bridging circuit shown is a Wheatstone bridge suitable for the situation of Figure II, where each strain gauge 4 is mounted in the same direction. The strain gauges 4 are in the form of resistors and a Wheatstone bridge bridge circuit is completed by a power source (battery) 11 and a measuring instrument 12 . This is a standard type of circuit, but other bridging circuit variations can also be used in conjunction with other embodiments having other strain gauge configurations.

在范围广泛的实施方案中,本发明的弹簧秤不限于单个部件或由半导体材料制成。此外,可以使用多种几何形状,只要通过至少三个将装载平台与周围框架相连的挠性弹簧悬挂中心装载平台即可。In its broadest embodiments, the spring balance of the present invention is not limited to a single component or made of semiconducting materials. Furthermore, a variety of geometries can be used as long as the central loading platform is suspended by at least three flexible springs connecting the loading platform to the surrounding frame.

另一实施方案是在框架中的圆形开口内的基本圆形的装载平台。曲线形的挠性杆或弹簧分别连接到装载平台和框架上。通常,接点彼此正对,但是它们可以在装载平台和框架之间的间隙中重叠,或甚至越过/沿着彼此盘旋。如前所述的应变仪位于挠性杆与框架或平台的接点处,即位于在称重操作中表面应力最强的点。Another embodiment is a substantially circular loading platform within a circular opening in the frame. Curved flexible rods or springs are attached to the loading platform and frame respectively. Typically, the joints are directly opposite each other, but they may overlap in the gap between the loading platform and the frame, or even hover over/along each other. Strain gauges as previously described are located at the junction of the flexible rod and the frame or platform, ie at the point where the surface stresses are strongest during the weighing operation.

另一可行的构造包括三角形装载平台和在装载平台和框架之间的三个挠性杆。位于例如三个接点的应变仪可以以改变的桥接方式连接。因此,多种几何形状均满足本发明的要求。Another possible configuration includes a triangular loading platform and three flexible bars between the loading platform and the frame. Strain gauges at, for example, three junctions can be connected in varying bridging fashion. Thus, a variety of geometries meet the requirements of the present invention.

带有四个挠性弹簧的构造是优选的,至少有三个原因:A configuration with four flex springs is preferred for at least three reasons:

1.在标准类型的惠斯登电桥中,正好包括四个电阻器。1. In a standard type of Wheatstone bridge, exactly four resistors are included.

2.为了具有稳定的装载平台,不应该使用过多的杆。2. In order to have a stable loading platform, too many poles should not be used.

3.对于用硅制成的微型秤,要注意硅(100)片具有四折对称,这要求压电电阻器沿着[011]或[011]方向放置。3. For microscales made of silicon, it should be noted that the silicon (100) sheet has four-fold symmetry, which requires piezoresistors to be placed along the [011] or [011] direction.

图IV示意性显示了穿过包含平台1的弹簧秤19的中心部分的横截面,在该平台上已经根据本发明的图I实施方案放置了样品容器。包含平台的中心区域相对于框架2变薄,框架2可以较厚。显示出了挠性杆3,其中从侧视图中可以看见两个杆,并且它们呈现S形。Figure IV schematically shows a cross-section through the central part of the spring balance 19 comprising the platform 1 on which sample containers have been placed according to the Figure I embodiment of the invention. The central area containing the platform is thinned relative to the frame 2, which may be thicker. The flexible rod 3 is shown, where two rods can be seen from the side view and they are S-shaped.

图IV中所示的实施方案还显示了任选的基底部件24,其可以由玻璃制成,并通过阳极结合连接到框架2上。通过使基底部件24延伸进入装载平台1的下方,其形成了装载平台1的下摆限度,作为挠性弹簧3的安全功能。如图所示,基底部件24还可以带有中心开口25以进行检查和清洁。在该秤上方,可以提供任选的顶盖26作为保护用的终点挡板和装载平台1的可能的上摆限度。任选地,在顶盖中有中心开口27,以使待称重的对象可以向下放到装载平台上。可以为出自应变仪的信号引线提供接触部件。顶盖可以是玻璃并固定到基底部件24上。The embodiment shown in Figure IV also shows an optional base member 24, which may be made of glass, and is attached to the frame 2 by anodic bonding. By extending the base part 24 below the loading platform 1 , it forms the hem limit of the loading platform 1 as a safety function of the flexible spring 3 . As shown, base member 24 may also have a central opening 25 for inspection and cleaning. Above the scale, an optional top cover 26 can be provided as a protective end stop and possible upper swing limit of the loading platform 1 . Optionally, there is a central opening 27 in the top cover to allow the object to be weighed to be lowered onto the loading platform. Contact parts can be provided for the signal leads from the strain gauges. The top cover may be glass and is secured to the base member 24 .

如图V所示,另一实施方案使用传感器19’和位于微量天平上的吊篮形式的样品容器。支架包含微量天平阵列,在该图中显示了一个微量天平的一部分。通过连接到微量天平上的环圈29和从环圈29到篮筐样品容器18’的线30将吊篮形式的样品容器18’从微量天平上悬挂下来。在这一实施方案中,吊篮样品容器、与微量天平的连接装置、以及用于连接连接装置和吊篮样品容器的装置可以是本领域已知的任何装置,其可以容纳样品并在质量分析条件下保持稳定。As shown in Figure V, another embodiment uses a sensor 19' and a sample container in the form of a hanging basket on a microbalance. The rack contains the array of microbalances, a portion of which is shown in this figure. The sample container 18' in the form of a hanging basket is suspended from the microbalance by a loop 29 attached to the microbalance and a wire 30 from the loop 29 to the basket sample container 18'. In this embodiment, the bucket sample container, the connection device to the microbalance, and the means for connecting the connection device to the bucket sample container can be any device known in the art that can hold the sample and perform the analysis during mass analysis. remain stable under conditions.

尽管质量分析优选使用应变仪、特别是如上所述在惠斯登电桥中的压电电阻器进行,但使用其它检测微量天平偏转的方法也在本发明的保护范围内。这些方法包括但不限于使用光检测器或磁检测器。在一个实施方案中,使用光检测器测定来自各个微量天平的偏转信号。Although mass analysis is preferably performed using strain gauges, especially piezoresistors in a Wheatstone bridge as described above, it is also within the scope of the invention to use other methods of detecting deflection of the microbalance. These methods include, but are not limited to, the use of photodetectors or magnetic detectors. In one embodiment, a light detector is used to measure the deflection signal from each microbalance.

在另一实施方案中,传感器19”是包含悬臂的微量天平;在图VI和VII中显示了两个例子。在图VI-A和VI-B中,悬臂31包含用于悬挂样品容器18’(其优选为吊篮)的环结构32。通过任何合适的方式、优选通过线30’将吊篮连接到悬臂31的环结构32的环上。悬臂的桥33包括压电电阻器形式的应变仪4,以对样品容器18’中放置的样品进行质量分析。In another embodiment, the sensor 19" is a microbalance comprising a cantilever; two examples are shown in Figures VI and VII. In Figures VI-A and VI-B, the cantilever 31 contains a (It is preferably a ring structure 32 of a gondola). The gondola is connected to the ring of the ring structure 32 of the cantilever 31 by any suitable means, preferably by a wire 30'. The bridge 33 of the cantilever comprises a strain in the form of a piezoresistor instrument 4 to perform mass analysis on the sample placed in the sample container 18'.

在图VII-A和VII-B中,传感器19是包括用于悬挂样品容器18’(其优选为吊篮)的吊索结构32’。通过任何合适的方式、优选通过线材30”将吊篮样品容器18’连接到悬臂31’的吊索构造32的吊索上。悬臂31’的桥33’包括压电电阻器形式的应变仪4’,以对样品容器18’中放置的样品进行质量分析。In Figures VII-A and VII-B, the sensor 19'' is comprised of a sling structure 32' for suspending the sample container 18', which is preferably a gondola. The gondola sample container 18' is connected to the sling of the sling construction 32 of the cantilever 31' by any suitable means, preferably by wire 30". The bridge 33' of the cantilever 31' comprises a strain gauge 4 in the form of a piezoresistor ', to perform mass analysis on the sample placed in the sample container 18'.

通过读取板读取来自微量天平的信号并用微型计算机处理。可以使用温度信号补偿传感器的温度依赖性。温度信号可以由独立的电阻器或二极管提供,或可以监测总桥路电阻。The signal from the microbalance is read by a readout plate and processed by a microcomputer. The temperature dependence of the sensor can be compensated for using the temperature signal. The temperature signal can be provided by a separate resistor or diode, or the total bridge resistance can be monitored.

在将样品加热或冷却的测量中,连接处的热电势会影响测量。这可以通过周期性地关闭电源11并从测量中扣除输出量来补偿。还可以使用复合交流(AC)激发(compound alternating current excitation)和锁定(lock-in)测量。In measurements where the sample is heated or cooled, the thermoelectric potential at the junction affects the measurement. This can be compensated by periodically switching off the power supply 11 and subtracting the output from the measurement. Compound alternating current excitation and lock-in measurements can also be used.

计算机配有合适的软件,用于设计试验、控制环境并获取和分析数据以测定样品特性。The computer is equipped with suitable software for designing experiments, controlling the environment, and acquiring and analyzing data to determine sample properties.

优选地,在受控环境中进行质量分析。在将样品和样品容器置于一个或多个合适的可密封室(其将样品容器与未受控环境条件隔离)中时,可以控制环境。要控制的环境条件包括但不限于压力、温度和流体组成,例如但不限于样品和样品容器周围的气体。合适的压力包括10-10托至300巴,优选10-6托至150巴;温度通常为-200至1000℃,更通常小于500℃。可以使用本领域已知的任何合适的加热或冷却设备控制温度。Preferably, mass analysis is performed in a controlled environment. The environment can be controlled when the sample and sample containers are placed in one or more suitable sealable chambers that isolate the sample containers from uncontrolled environmental conditions. Environmental conditions to be controlled include, but are not limited to, pressure, temperature, and fluid composition, such as, but not limited to, the atmosphere surrounding the sample and sample containers. Suitable pressures include 10 −10 Torr to 300 bar, preferably 10 −6 Torr to 150 bar; temperatures are typically -200 to 1000°C, more typically less than 500°C. The temperature can be controlled using any suitable heating or cooling device known in the art.

为了将样品称重并进行下述试验,可以改变受控环境中的流体介质的组成。在是流体介质的情况下,合适的气体包括但不限于氮;一氧化碳;二氧化碳;氨;SF6;氩气、氦气或其它惰性气体以及丁烷、戊烷或其它烃类中的一种或多种。The composition of the fluid medium in the controlled environment can be varied in order to weigh the samples and conduct the tests described below. In the case of a fluid medium, suitable gases include, but are not limited to, nitrogen; carbon monoxide; carbon dioxide; ammonia; SF 6 ; Various.

通常,随时间改变环境条件以如下所述测定样品特性。改变可以包括温度的显著改变、压力改变和组成环境的改变中的一种或多种。例如,可以通过下列步骤测定一种或多种特性:首先测量来自样品阵列的输出信号,然后改变该样品阵列的环境条件,然后测量来自样品阵列的第二输出信号,并通过比较第一和第二输出信号测定各样品的一种或多种特性。可以在受试样品上通过下列次序重复这些步骤:然后将受试样品阵列暴露在进一步改变的环境条件中,然后测量来自样品阵列的进一步输出信号,并通过比较来自进一步试验的输出信号确定各样品的一种或多种特性。可以在环境条件变化之前和之后比较微量天平阵列的偏转信号。优选地,对于多个弹簧秤的每一个,使用已知的传感器曲线实现这一点。Typically, environmental conditions are varied over time to determine sample properties as described below. Changes may include one or more of significant changes in temperature, changes in pressure, and changes in the compositional environment. For example, one or more properties can be determined by first measuring the output signal from the sample array, then varying the environmental conditions of the sample array, then measuring a second output signal from the sample array, and by comparing the first and second Two output signals determine one or more properties of each sample. These steps can be repeated on the test sample in the following order: then exposing the test sample array to further altered environmental conditions, then measuring further output signals from the sample array, and determining by comparing the output signals from further experiments One or more properties of each sample. The deflection signals of the microbalance array can be compared before and after changes in environmental conditions. Preferably, this is accomplished using known sensor curves for each of the plurality of spring balances.

也可以通过记录负载天平的特征频率并根据公式 (其中k是弹簧刚度,且m是有效质量)将其联系起来,由此测量质量。可以通过整个阵列的外部激发引发振动,然后监测各天平的自由振荡。当在转换器输出上叠加大的偏移(例如通过热电效应)时,该方法可用于校准或测量。It can also be recorded by recording the characteristic frequency of the load balance and according to the formula (where k is the spring rate, and m is the effective mass) to relate this, thereby measuring the mass. Vibrations can be induced by external excitation of the entire array and then the free oscillation of the individual balances monitored. This method can be used for calibration or measurement when a large offset is superimposed on the converter output (for example by the pyroelectric effect).

用途use

除了样品称重外,本发明的微量天平还可以具有一种或多种不同的用途。例如,监测由环境变化引起的或随时间引起的样品重量变化,可以尤其产生表面积、孔径大小和体积、酸度/碱度和金属官能方面的数据。可以监测由样品的质量变化引起的环境变化,且微量天平可用于反应性测试。In addition to sample weighing, the microbalance of the present invention may also have one or more different uses. For example, monitoring changes in sample weight caused by environmental changes or over time can yield data on, inter alia, surface area, pore size and volume, acidity/basicity, and metal functionality. Environmental changes caused by changes in the mass of the sample can be monitored, and a microbalance can be used for reactivity testing.

微量天平阵列本身可用于将样品阵列的样品称重。可以使用这种功能作为另一操作(例如表征分析、反应性试验或合成)的准备步骤。此外,重量变化本身可以单独作为涉及使一组样品暴露在特定条件组下的分析(例如用于反应性试验的焦炭沉积、高压下的氢吸收)的关键部分。其它可行的用途包括但不限于:The microbalance array itself can be used to weigh samples of the sample array. This functionality can be used as a preparatory step for another operation such as characterization, reactivity testing or synthesis. Furthermore, the weight change itself can be a critical part of an analysis involving exposing a set of samples to a specific set of conditions (eg coke deposition for reactivity tests, hydrogen absorption at high pressure). Other possible uses include, but are not limited to:

来自物理吸附的探针分子的等温线:Isotherms from physisorbed probe molecules:

●表面积●Surface area

使用朗缪尔方程(单层吸附)或BET(Brunauer,Emmett和Teller)方程(多层吸附)或任何其它合适的测定或计算方法由等温线数据推算出表面积。通常,使用氮作为被吸附物。Surface area is extrapolated from isotherm data using the Langmuir equation (single layer adsorption) or the BET (Brunauer, Emmett, and Teller) equation (multilayer adsorption) or any other suitable method of measurement or calculation. Typically, nitrogen is used as the adsorbate.

●孔体积●Pore volume

使用Kelvin方程,将被吸附物的量表示成相应的孔体积。The amount of adsorbate was expressed as the corresponding pore volume using the Kelvin equation.

●孔径分布●Pore size distribution

通常,将吸附等温线以及Kelvin方程以各种方式合并,以估算作为分压函数的被吸附物膜厚。使用这些方程估算样品的孔径分布。Typically, adsorption isotherms and the Kelvin equation are combined in various ways to estimate adsorbate film thickness as a function of partial pressure. Use these equations to estimate the pore size distribution of the sample.

●吸附能力●Absorptive capacity

对于给定条件组(蒸气压和温度),测量被吸附的探针分子的量。该值可用于评测或比较材料。典型例子是选择性吸附和气体储存应用。同样有关的是使用一组具有各种动力直径的探针分子的单种吸附剂的吸附能力。这与McBain测量类似并有助于将材料的孔径大小分级。For a given set of conditions (vapor pressure and temperature), the amount of adsorbed probe molecules is measured. This value can be used to rate or compare materials. Typical examples are selective adsorption and gas storage applications. Also of interest is the adsorption capacity of a single adsorbent using a set of probe molecules with various kinetic diameters. This is similar to the McBain measure and helps to grade the pore size of the material.

●吸附动力(扩散)● Adsorption kinetics (diffusion)

通过测量探针气体的吸收速率,可以估算吸附剂/被吸附物体系的扩散常数。当在温度范围内进行时,该方法可用于测定扩散的活化能。By measuring the rate of uptake of the probe gas, the diffusion constant of the adsorbent/adsorbate system can be estimated. When performed over a temperature range, this method can be used to determine the activation energy of diffusion.

●吸附热●Adsorption heat

在数个温度的测量吸附能够计算给定样品和被吸附物的吸附热。Measurement of adsorption at several temperatures enables calculation of the heat of adsorption for a given sample and adsorbate.

来自化学吸附的探针分子的等温线:Isotherms from chemisorbed probe molecules:

●酸度●acidity

可以使用被样品吸附的探针碱的量估算样品的酸位点的数。通过在数个温度进行吸附测量、或通过测量解吸的碱的量(其为温度的函数),可以估测样品的酸强度分布。The number of acid sites of the sample can be estimated using the amount of probe base adsorbed by the sample. The acid strength distribution of the sample can be estimated by performing adsorption measurements at several temperatures, or by measuring the amount of base desorbed as a function of temperature.

探针分子的例子:NH3、CO、吡啶、三甲基膦Examples of probe molecules: NH 3 , CO, pyridine, trimethylphosphine

○酸位点的数○Number of acid sites

○酸位点的强度○Strength of acid sites

●碱度● Alkalinity

与酸度类似地,但是使用表征碱度的探针分子。Similar to acidity, but using a probe molecule that characterizes alkalinity.

探针分子的例子:乙烯、丙烯、1-丁烯Examples of probe molecules: ethylene, propylene, 1-butene

○碱性位点的数○Number of basic sites

○碱性位点的强度○Strength of basic sites

●金属官能●Metallic function

通过选择合适的探针分子,可以表征样品上负载的金属。如果样品上负载的金属量未知,可以使用被含有金属官能的材料吸附的探针分子的量测定暴露的金属原子的量。如果金属负载量已知,该相同信息可用于测定百分之几的金属可用于催化反应。这种类型的信息对于表征作为浸渍条件的函数的金属分散性、二次处理(例如水热)、和碳沉积引起的失活是非常有用的。By selecting appropriate probe molecules, the metals loaded on the sample can be characterized. If the amount of metal loaded on the sample is unknown, the amount of probe molecules adsorbed by the metal-functional containing material can be used to determine the amount of exposed metal atoms. If the metal loading is known, this same information can be used to determine what percent of the metal is available to catalyze the reaction. This type of information is very useful for characterizing metal dispersion as a function of impregnation conditions, secondary treatments (eg hydrothermal), and deactivation due to carbon deposition.

由于样品上金属的氧化还原而产生的样品质量变化也可用于表征金属含量、分散性和活性。Changes in sample mass due to redox of metals on the sample can also be used to characterize metal content, dispersion, and activity.

○CO吸收○CO absorption

○H2S吸收○H 2 S absorption

○H2/O2氧化还原/吸收○H 2 /O 2 redox/absorption

大气取样atmospheric sampling

可以将一组材料置于微量天平阵列中,并暴露在工艺流或来自周围环境的气体下,以表征工艺流或气体。一个例子是选择涵盖一定孔径范围的一组多孔材料。每种独特材料仅吸附特定尺寸范围的分子。通过同时比较每一样品的吸收量,可以表征气流。A set of materials can be placed in a microbalance array and exposed to a process stream or gas from the ambient environment to characterize the process stream or gas. An example is the selection of a set of porous materials covering a range of pore sizes. Each unique material only adsorbs molecules in a specific size range. By comparing the uptake of each sample simultaneously, airflow can be characterized.

类似地,也可以使用含有已知改变吸附性质的特定阳离子的材料表征气流。Similarly, gas streams can also be characterized using materials containing specific cations known to alter adsorption properties.

反应脉冲实验Response Pulse Experiment

●焦化●Coking

可以使反应剂流在一组样品上脉动,并可以测量对于给定脉冲的沉积碳量。这为一组样品提供了关于反应性和失活速率的数据。The reactant flow can be pulsed over a set of samples and the amount of deposited carbon for a given pulse can be measured. This provides data on reactivity and inactivation rates for a set of samples.

●氧化还原● redox

使一组样品暴露在氧化和/或还原环境中,同时测量重量变化,这产生关于氧化还原活性和能力的信息。这与上述金属试验类似。Exposing a set of samples to an oxidizing and/or reducing environment while measuring the weight change yields information about redox activity and capacity. This is similar to the metal test above.

●聚合● aggregation

可以通过使聚合催化剂或引发剂暴露在可低聚或可聚合气体中来评估关于这些材料的活性和动力的信息。Information about the activity and kinetics of these materials can be assessed by exposing polymerization catalysts or initiators to oligomerizable or polymerizable gases.

组合技术Combination technology

用于就地分析一组样品的性质的两种或多种技术的组合是本发明的特别有价值的特征。The combination of two or more techniques for in situ analysis of properties of a set of samples is a particularly valuable feature of the invention.

●IR温度记录+微量天平测量●IR temperature record + micro balance measurement

微量天平测量可以与IR温度记录测量结合。在这种实验中,在样品阵列中加入碱(或酸)。在暴露过程中,微量天平监测重量变化,IR相机监测热变化和吸附热。两种技术的同时使用提供了比单独使用每种技术多得多的信息。来自两种测量的信息可以合并以测定材料中酸(或碱)位点的数和强度。Microbalance measurements can be combined with IR thermographic measurements. In this experiment, a base (or acid) is added to the sample array. During the exposure, a microbalance monitors weight changes and an IR camera monitors thermal changes and heat of adsorption. The simultaneous use of both techniques provides much more information than each technique alone. Information from both measurements can be combined to determine the number and strength of acid (or base) sites in the material.

○酸度○Acidity

○碱度○ Alkalinity

○反应性○Reactivity

●温度+微量天平测量●Temperature + micro balance measurement

监测作为温度的函数的重量变化,该体系可以用作combi-tga(热解重量分析)。可以监测例如作为温度的函数的水解吸之类的现象、沸石的模板氧化(在温度变化过程中通入空气)、用于再生研究的碳燃烧动力。Monitoring the weight change as a function of temperature, the system can be used as combi-tga (thermogravimetric analysis). Phenomena such as water desorption as a function of temperature, template oxidation of zeolites (airing during temperature changes), carbon combustion kinetics for regeneration studies can be monitored.

●XRD+微量天平测量。●XRD + micro balance measurement.

微量天平测量可以与combi-xrd(x-射线衍射)测量结合。在该体系中,可以使一组样品暴露在探针气体中,这可以测量作为被吸附探针气体量的函数的结构信息。一些应用例子可以是:Microbalance measurements can be combined with combi-xrd (x-ray diffraction) measurements. In this system, a set of samples can be exposed to a probe gas, which allows the measurement of structural information as a function of the amount of probe gas adsorbed. Some application examples could be:

○水对单位孔度(unit cell size)的影响○Effect of water on unit cell size

○给定烃对单位孔度的影响○ Effect of given hydrocarbon on unit pore size

○碳(焦炭)对单位孔度的影响(就地焦炭燃烧)○ Effect of carbon (coke) on unit pore size (in-situ coke combustion)

上述描述和例子在不限制本发明范围的情况下举例说明本发明。有经验的操作者容易理解如何针对本发明的其它实施方案外推本公开的参数。本发明仅受本文所列的权利要求的限制。The above description and examples illustrate the invention without limiting the scope of the invention. A skilled operator will readily understand how to extrapolate the disclosed parameters for other embodiments of the invention. The invention is limited only by the claims set forth herein.

Claims (10)

1. in an array sample each is carried out the device of quality analysis, it comprises that an array independently holds the shuttle (18 of sample, 18 '), place these containers and make itself and a plurality of sensor (19,19 ', 19 ", 19 ) interact, described sensor provides the output signal of the qualitative data that comprises this sample array.
2. the device of claim 1, wherein said a plurality of sensors (19,19 ', 19 ", 19 ) comprise the microbalance array.
3. the device of claim 2, wherein the microbalance array comprises spring scale array (19).
4. the device of claim 3, wherein spring scale array (19) is whole with the framework of making by micro-cutting work sheet block of material (2).
5. the device of claim 3, wherein each spring scale (19) comprises the loading platform (1) that hangs with one or more flexible spring (3), and each spring scale (19) is equipped with the bridge joint deformeter (4) of strain on each the side that is used to measure described one or more flexible spring (3).
6. the device of claim 5, wherein each described deformeter (4) is a piezoresistor.
7. each device of claim 2-6 is wherein placed shuttle array (18,18 ') it is contacted with the microbalance array.
8. each device of claim 2-6, wherein shuttle array (18 ') comprises the basketry array that is suspended on the microbalance array.
9. each device of claim 2-6 further comprises being used for the compound AC signal generator of the frequency detecting deviation signal of coding and having the wave filter (11,12) of lock-in amplifier.
10. use each the method for device of claim 1-6, comprise the following steps:
(a) an array sample is placed an array independently in the shuttle (18,18 ');
(b) place these independently shuttle (18,18) itself and a plurality of sensor (19,19 ', 19 ", 19 ) are interacted, described sensor provides the output signal of the qualitative data that comprises this sample array; With
(c) determine the quality of each sample according to output signal.
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US20070245840A1 (en) 2007-10-25
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WO2006007593A1 (en) 2006-01-19
JP2008505323A (en) 2008-02-21

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